Synthesis,characterization, and electroluminescence of PPV copolymers containing electron and hole‐transporting units

Three series of poly(phenylene vinylene) (PPV) derivatives containing hole‐transporting triphenylamine derivatives [N‐(4‐octoxylphenyl)diphenylamine, N,N′‐di(4‐octyloxylphenyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine, and N,N′‐di(4‐octoxylphenyl)‐N,N′‐diphenylbenzidine] (donor) and electron‐transporting oxadiazole unit (2,5‐diphenyl‐1,3,4‐oxadiazole) (acceptor) in the main chain were synthesized by improved Wittig copolymerization. The resulting donor–acceptor (D‐A) polymers are readily soluble in common organic solvents, such as chloroform, dichloroethane, THF, and toluene. The polymers containing oxadiazole group exhibit good thermal stability with 5% weight loss above 400 °C. The intramolecular charge‐transfer was observed in these D‐A polymers. In comparison with corresponding polymers without oxadiazole unit, the single‐layer devices based on the D‐A polymers showed much improved electroluminescent properties, because of the balanced charge injection and transport. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1566–1576, 2008     

Synthesis and ion‐sensing phenomena of two new helical conjugated oligomers containing 1,10‐phenanthroline and oligo‐alkylthiophene

Two new 1,10‐phenanthroline (Phen) containing conjugated oligomers, oligo‐3,8‐bis(4‐octylthiophene‐2‐yl)‐1,10‐phenanthroline) (PDTPh) and oligo‐3,8‐bis‐(4‐octyl‐5‐(4‐ctylthiophene‐2‐yl)thiophene‐2‐yl)‐1,10‐phenanthroline) (PTTPh), as well as their corresponding monomers (OTPhOT and OTOTPhOTOT) were prepared and their metal ion‐sensing properties were investigated. The oligomers showed high thermal stability, good proccessibility, and gave varied color when reacted with different metal ions. Oligomers also showed distinct responses toward metal ions when compared with their corresponding monomers, suggesting that the ionochromic responses were determined by not only the coordinating ability of Phen unit but also the conformation of oligomer chains. Moreover, the differences in the ion‐sensing behaviors between OTPhOT and OTOTPhOTOT also suggested that the coordination ability of Phen depends on its substituents. The oligo‐alkylthiophene moieties in PDTPh and PTTPh acted as spacers to reorganize the conformation of the oligomer chains, as well as the electron donating groups to adjust the coordination ability of the Phen. These findings provide a clue for designing Phen‐containing ion‐sensors for specified ion‐sensing applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1586–1597, 2008     

Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors

This review article focuses primarily on the work carried in our laboratories over the last few years using luminescent and colorimetric sensors, where the anion recognition occurs through hydrogen bonding in organic or aqueous solvents. This review begins with the story of the discovery of fluorescent photoinduced electron transfer (PET) sensors for anions using charged neutral urea or thiourea receptors where both fluorescent and NMR spectroscopic methods monitored anion recognition. This work led to the development of dual luminescent and colorimetric anion sensors based on the use of the ICT based naphthalimide chromophore, where ions such as fluoride gave rise to changes in both the fluorescence and the absorption spectra of the sensors, but at different concentrations. Here, the former changes were due to hydrogen bonding interactions, whereas the latter was due to the deprotonation of acidic protons, giving rise to the formation of the bifluoride anion (HF₂⁻). Modification of the 4-amino-l,8-naphthalimide moiety has facilitated the formation of colorimetric anion sensors that work both in organic or aqueous solutions. Such charge neutral receptor motifs have also been incorporated into organic scaffolds with norbomyl and calixarene backbones, which have enabled us to produce anion directed self-assembled structures.     

Radiation induced luminescence processes in c-BN

Spectral properties of cubic boron nitride have been studied using methods of photoluminescence (PL), X-ray excited luminescence (XL), thermoluminescence (TL) and optically stimulated luminescence. It is found that emission of cubic boron nitride is presented by 4 subbands, their relative yield is determined by the excitation type: blue, green (dominant) and red bands are observed in PL, ultraviolet, blue (dominant), green and red bands—in XL. Three thermal peaks are found in TL curves in the 0–700°C temperature range, their presence and intensity depend on radiation type used. A tentative correspondence between thermal peaks and emission bands is found.     

Photoluminescence spectra of copper-based planar nanostructures

We have studied the luminescence of planar nanostructures based on amorphous copper, excited by a low-intensity source in the UV region of the spectrum. We have shown that it is dependent on the packing density of copper granules on the surface of the quartz substrate, the presence of chains of granules, the optical properties of the surrounding medium, and the oxidation time. The observed maxima at the wavelengths of 400 nm and 520 nm correspond to luminescence of the quartz and copper oxide Cu₂O. The maximum at 650 nm is located in the region of plasma resonances of the oxidized copper chains and aggregates, and is enhanced in the “hot spot” region near the surface of interacting copper particles. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 510–515, July–August, 2006.     

Cluster model for complex compounds of hexavalent uranium

We have studied the regular patterns of the change in the electronic transition frequency in low-temperature luminescence spectra of uranyl trinitrate and tetranitrate crystals with alkali metal cations or an NH ₄ ⁺ group as the outer-sphere cations, as a function of the ionization potential of the latter. An analogous study was carried out as a function of the ratio of the concentrations of impurity and matrix for different cations in mixed crystals and solid solutions. Analysis of the results obtained, together with available crystallographic data, allowed us to propose a cluster model for the uranyl complex. The observed regular patterns are also explained from the standpoint of statistical thermodynamics. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 588–591, September–October, 2006.     

高压对以沸石分子筛基质的Eu（Ⅲ）稀土发光材料荧光光谱影响的研究

 本文研究了高压下无机微孔材料的相转变，并讨论了压力对离子交换的Eu（Ⅲ）NaA和Eu（Ⅲ）NaY两种以沸石分子筛为基质的稀土发光材料发光性质的影响。实验结果表明，对于不同基质材料，压力对Eu（Ⅲ）离子的光谱结构的影响，尤其是对⁵D₀→⁷F₁磁偶极跃迁与⁵D₀→⁷F₂电偶极跃迁强度比（I_m/I_e）的影响十分显著。对于Eu（Ⅲ）NaA样品来说，I_m/I_e值随压力的增加而增加，而对于Eu（Ⅲ）NaY样品，I_m/I_e值随压力的增加而减少。     

Synthesis of fluorine-containing tetraketones and diketo esters and luminescence-spectral properties of their complexes with lanthanide ions

The Claisen condensation of diesters of fluorinated dicarboxylic acids with 2-acetyl-naphthalene affords the corresponding naphthyl-containing tetraketones and diketo esters. The luminescence-spectral properties and stability constants of complexes of these compounds with Eu³⁺ ions were estimated. The characteristics of the complexes are comparable with those of fluorinated β-diketones containing chromophoric substituents, which are widely used in luminescence analysis. The synthesized naphthyl-containing diketo esters are efficiently conjugated with proteins and can be used for detection of biospecific interactions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 269—273, February, 2006.     

稀土铒离子注入多孔硅的发光

稀土离子Er注入多孔硅中.在350keV能量,1×1012~1×1015/cm2剂量范围内,注入后的多孔硅仍保持明亮的可见光发射.退火后,在近红外区测到1.54μm附近Er3+的特征发射.其发射强度比硅单晶对照样品明显增强,实验表明这增强作用来源于多孔硅的表面发光层.电化学制备过程中在表面层中带入的O、C、F等多种杂质可能是Er3+发光增强的原因.